Phase change inks

ABSTRACT

Disclosed is a phase change ink composition comprising a phase change ink carrier and a colorant compound of the formula  
                 
 
wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1, 2, 3, or 4, R 1  is an alkylene group, an arylene group, an arylalkylene group, or an alkylarylene group, provided that no oxygen atom creates a  
                 
 
linkage, X is —O— or —NR 3 — wherein R 3  is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, and R 2  is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group.

CROSS-REFERENCE TO RELATED APPLICATIONS

Copending Application U.S. Ser. No. 10/260,146, filed Sep. 27, 2002,entitled “Colorant Compounds,” U.S. Publication 20040077887, with thenamed inventors Jeffery H. Banning and C. Wayne Jaeger, the disclosureof which is totally incorporated herein by reference, disclosescompounds of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group or an arylalkylene group, and X is(a) a hydrogen atom, (b) a group of the formula

wherein R₂ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, (c) an alkyleneoxy, aryleneoxy, arylalkyleneoxy, oralkylaryleneoxy group, or (d) a group of the formula

wherein R₄ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group.

Copending Application U.S. Ser. No. 10/260,376, filed Sep. 27, 2002,U.S. Publication 20040102540, entitled “Phase Change Inks,” with thenamed inventors C. Wayne Jaeger and Jeffery H. Banning, the disclosureof which is totally incorporated herein by reference, discloses a phasechange ink composition comprising a phase change ink carrier and acolorant compound of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group or an arylalkylene group, and X is(a) a hydrogen atom, (b) a group of the formula

wherein R₂ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, (c) an alkyleneoxy, aryleneoxy, arylalkyleneoxy, oralkylaryleneoxy group, or (d) a group of the formula

wherein R₄ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group.

Copending Application U.S. Ser. No. 10/260,379, filed Sep. 27, 2002,U.S. Publication 20040082801, entitled “Methods for Making ColorantCompounds,” with the named inventors C. Wayne Jaeger and Jeffery H.Banning, the disclosure of which is totally incorporated herein byreference, discloses a process for preparing a colorant of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group or an arylalkylene group, R₂ is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and R₄ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, can be prepared by a process which comprises (a)preparing a first reaction mixture by admixing (1) leucoquinizarin and,optionally, quinizarin, (2) an aminobenzene substituted with an alcoholgroup of the formula —R₁—OH, (3) boric acid, and (4) an optionalsolvent, and heating the first reaction mixture to prepare analcohol-substituted colorant of the formula

followed by (b) converting the colorant thus prepared to either (i) anester-substituted colorant by reaction with an esterification compoundwhich is either (A) an anhydride of the formula

or (B) an acid of the formula R₂COOH in the presence of an optionalesterification catalyst, or (ii) a urethane-substituted colorant byreaction with an isocyanate compound of the formulaR₄—N═C═Oand (c) brominating the colorant thus prepared, wherein eitherconversion to ester or urethane can be performed before bromination orbromination can be performed before conversion to ester or urethane.

Copending Application U.S. Ser. No. ______; Attorney Docket No.A3384-US-NP), filed concurrently herewith, entitled “ColorantCompounds,” with the named inventors Jeffery H. Banning, Wolfgang G.Wedler, and C. Wayne Jaeger, the disclosure of which is totallyincorporated herein by reference, discloses a colorant compound of theformula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group, an arylene group, an arylalkylenegroup, or an alkylarylene group, provided that no oxygen atom creates a

linkage, X is —O— or —NR₃— wherein R₃ is a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, or an alkylaryl group, and R₂is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group.

BACKGROUND

Disclosed herein are phase change inks. More specifically, disclosedherein are hot melt or phase change inks containing specific colorantcompounds. One embodiment is directed to a phase change ink compositioncomprising a phase change ink carrier and a colorant compound of theformula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group, an arylene group, an arylalkylenegroup, or an alkylarylene group, provided that no oxygen atom creates a

linkage, X is —O— or —NR₃— wherein R₃ is a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, or an alkylaryl group, and R₂is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labelling.

Phase change inks are desirable for ink jet printers because they remainin a solid phase at room temperature during shipping, long term storage,and the like. In addition, the problems associated with nozzle cloggingas a result of ink evaporation with liquid ink jet inks are largelyeliminated, thereby improving the reliability of the ink jet printing.Further, in phase change ink jet printers wherein the ink droplets areapplied directly onto the final recording substrate (for example, paper,transparency material, and the like), the droplets solidify immediatelyupon contact with the substrate, so that migration of ink along theprinting medium is prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 6,395,078 (Jaeger), U.S. Pat. No. 6,422,695 (Jaeger),Canadian Patent Publication 2 355 533 (filed Aug. 20, 2001, publishedFeb. 23, 2002), European Patent Publication EP 1 182 232 (filed Aug. 17,2001, published Feb. 27, 2001), Japanese Patent Publication JP2002129044 (filed Aug. 8, 2001, published May 9, 2002), Brazilian PatentPublication P101035819 (filed Aug. 22, 2001, published Mar. 26, 2002),and Mexican Patent Application 2001008418 (filed Aug. 20, 2001), thedisclosures of each of which are totally incorporated herein byreference, disclose a compound having the formula

wherein at least one Q₁, Q₂, Q₃, and Q₄ is a halogen atom and any of Q₁,Q₂, Q₃ and Q₄ which is not a halogen atom is a hydrogen atom; andwherein R comprises at least two carbon atoms. The invention furtherencompasses inclusion of such compound into phase change ink carriercompositions, as well as printing methods utilizing such compound.

British Patent Publication GB 2 021 138 (Hohmann et al.), the disclosureof which is totally incorporated herein by reference, discloses mixturesof dyestuffs of the formula

and of the formula

wherein R₁, R₂, and R₃ denote C₁-C₄ alkyl, C₁-C₄ alkoxy, or halogen, andn denotes 2 or 3, which are suitable for dyeing polyester fibers by theexhaustion process. Dark blue and navy blue dyeings with good fastnessproperties are obtained.

U.S. Pat. No. 6,174,937 (Banning et al.), the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomprising a material of the formula

wherein X₁, X₂, X₃ and X₄ are segments comprising atoms selected fromgroups V and VI of the periodic table; wherein at least one R₁ and R₅comprises at least 37 carbon units; and wherein R₂, R₃ and R₄ eachcomprise at least one carbon unit. The invention further encompasses acomposition of matter, as well as methods of reducing coefficients offriction of phase change ink formulations.

U.S. Pat. No. 5,507,864 (Jaeger et al.), the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomposition that includes a combination of different dye types such asan anthraquinone dye and a xanthene dye, which is most preferably arhodamine dye. While each dye type is insufficiently soluble withrespect to favored carrier compositions to preserve color saturation inreduced ink quantity prints, the dye type combination permits increaseddye loading and maintains print quality. In a preferred embodiment ofthe invention, a favored carrier composition is adjusted to promote thecolored form of a preferred rhodamine dye (C.I. Solvent Red 49) andmixed with a preferred anthraquinone dye (C.I. Solvent Red 172) whoseconcentration is kept below a critical level to prevent post printedblooming. The resulting preferred phase change ink compositions providea magenta phase change ink with enhanced light fastness and colorsaturation, as well as good compatibility with preferred existingsubtractive primary color phase change inks.

U.S. Pat. No. 5,902,841 (Jaeger et al.), the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomposition wherein the ink composition utilizes a colorant incombination with a selected phase change ink carrier compositioncontaining at least one hydroxy-functional fatty amide compound.

R. Butnaru et al., “Researches on Dyeing of Cotton Fabrics with AcidDyestuffs, Concomitantly with Crease-Resist Treatments,” Cellulose Chem.Technol., 29, p. 471 (1995), the disclosure of which is totallyincorporated herein by reference, discloses an analysis of the resultsobtained on dyeing of cotton cellulosic fabrics with acid dyestuffs, onemploying crease-resist agents with polyfunctional structure. Theconclusion was reached that no chemical or physical bonds occur betweendyestuffs and the fiber, the dyestuffs being fixed onto the resin'saminic groups formed as a result of the thermal, crease-resisttreatment. Washing resistance of the cellulosic materials thus dyedattained the values obtained as a result of dyeing with directdyestuffs, specific for these types of fibers.

U.S. Pat. No. 6,235,094 (Banning et al.), the disclosure of which istotally incorporated herein by reference, discloses a compound havingthe formula

wherein R₁, Z and the carbonyl can be comprised by a common ring,wherein R₁ comprises a chromophore that absorbs light from the visiblewavelength range, and wherein n is an integer that is at least 12. Theinvention also encompasses a solid phase change ink composition. Suchcomposition includes a phase change ink carrier and a colorant. Thecolorant comprises a chromophore that absorbs light from the visiblewavelength range, and has the formula

wherein R₁, Z and the carbonyl can be comprised by a common ring,wherein n is an integer that is at least 12. Additionally, the inventionencompasses a method of forming a colorant. A first compound having theformula

is reacted with a second compound having the formula Z(CH₂)_(n)CH₃,wherein n is an integer that is at least 12, to form a third compoundhaving the formula

wherein the third compound comprises a chromophore that absorbs lightfrom the visible wavelength range.

U.S. Pat. No. 3,734,934 (Kolliker et al.), the disclosure of which istotally incorporated herein by reference, discloses dyestuffs of theformula

wherein W is chlorine, bromine, cyano, lower alkyl, lower alkoxy,carbonyl, phenoxycarbonyl, lower alkylthio, phenylthio, lower alkylsulfonyl, or a grouping of the formula

wherein Z is —CO— or —SO₂— and R₁ and R₂ are each independently hydrogenor lower alkyl, Y is lower alkylene, —CH₂CH₂OCH₂CH₂—, or—CH₂CH₂CH₂OCH₂CH₂CH₂—, X is a direct bond, —O—, —S—, —NH—, —COHN—, or—SO₂NH—, R″ is lower alkyl, cyclohexyl, phenyl, or phenyl substituted bychlorine, lower alkyl, or lower alkoxy, or bromine, the nucleus B iseither unsubstituted or further monosubstituted by chlorine, loweralkyl, or lower alkoxy, E is NH₂, OH, or NHT, and T is lower alkyl,cyclohexyl, phenyl, lower alkyl phenyl, or phenoxyphenyl.

British Patent 687,807, the disclosure of which is totally incorporatedherein by reference, discloses hydroxyethoxymethylphenyl-amino-anthraquinone dyestuffs and derivatives thereof of theformula

wherein X is hydrogen or methyl, R is hydrogen or CH₃OCH₂CH₂OZ, Z ishydrogen, hydroxy alkyl, or alkoxy alkyl, and Y is hydrogen, hydroxy, or

These compounds exhibit substantially enhanced substantivity for acetaterayon and have the ability to withstand the action of acid gas fumessuch as the combustion products of industrial and engine fuels.

Japanese Patent Publication 63223064, the disclosure of which is totallyincorporated herein by reference, discloses a blue coloring material foruse in optical filters which is of the formula

wherein R₁ to R₃ are each H, alkyl, alkoxy alkyl, hydroxy alkyl, orhalogen, R₄ is acyl, (alkyl)carbamoyl, arylcarbamoyl, aralkylcarbamoyl,alkenylcarbamoyl, methanesulfonyl, or H, X is alkylene,alkylene-O-alkylene, or alkylene-S-alkylene, and n is 1 or 2. An exampleis 1-{4-(2-benzoyloxyethyl)anilino}-4-hydroxyanthraquinone.

While known compositions and processes are suitable for their intendedpurposes, a need remains for improved colorant compounds. In addition, aneed remains for colorant compositions particularly suitable for use inphase change inks. Further, a need remains for colorant compounds with adesirable magenta color. Additionally, a need remains for colorantcompounds with desirable thermal stability. There is also a need forcolorant compounds with good lightfastness. In addition, there is a needfor colorant compounds that exhibit desirable solubility characteristicsin phase change ink carrier compositions. Further, there is a need forcolorant compounds that, when incorporated into phase change inks,exhibit reduced migration within a layer of printed ink. Additionally,there is a need for colorant compounds that, when incorporated intophase change inks, exhibit reduced crystallization within a layer ofprinted ink. A need also remains for colorant compounds that, whenincorporated into phase change inks, enable production of prints thatmaintain uniform color over long periods of time without unevenness orblotching. In addition, a need remains for colorant compounds that, whenincorporated into phase change inks, enable production of prints thatretain their original color over long periods of time. Further, a needremains for colorant compounds that, when incorporated into phase changeinks, enable production of prints that exhibit reduced sensitivity toimage discoloration upon contact with human fingertips. Additionally, aneed remains for colorant compounds that can be incorporated into phasechange inks in desirably high concentrations. There is also a need forcolorant compounds that can be manufactured easily and practically. Inaddition, there is a need for colorant compounds that can easily beconverted to derivative molecules thereof. Further, there is a need forcolorant compounds that can be derivatized with a desirable degree ofversatility.

SUMMARY

Disclosed herein is a phase change ink composition comprising a phasechange ink carrier and a colorant compound of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group, an arylene group, an arylalkylenegroup, or an alkylarylene group, provided that no oxygen atom creates a

linkage, X is —O— or —NR₃— wherein R₃ is a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, or an alkylaryl group, and R₂is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group.

DETAILED DESCRIPTION

The phase change ink compositions disclosed herein contain colorantcompounds of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is (i) an alkylene group (including linear, branched,saturated, unsaturated, cyclic, substituted, and unsubstituted alkylenegroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkylene group, provided that no oxygen atom creates a

linkage), in one embodiment with at least about 1 carbon atom, and inone embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 20 carbon atoms, in yet anotherembodiment with no more than about 6 carbon atoms, in still anotherembodiment with no more than about 2 carbon atoms, and in anotherembodiment with exactly 1 carbon atom, although the number of carbonatoms can be outside of these ranges, (ii) an arylene group (includingunsubstituted and substituted arylene groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the arylene group, provided that nooxygen atom creates a

linkage), in one embodiment with at least about 5 carbon atoms, and inanother embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 20 carbon atoms, in yet anotherembodiment with no more than about 7 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as phenyl or thelike, (iii) an arylalkylene group (including unsubstituted andsubstituted arylalkylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl portion and thealkyl portion of the arylalkylene group, provided that no oxygen atomcreates a

linkage), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 20 carbon atoms, in yet anotherembodiment with no more than about 7 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzyl,phenylethyl, and the like, including (a) arylalkylene groups whereinboth the aryl and the alkyl portions form the linkage between the

moiety and the

moiety, such as

and the like, and (b) arylalkylene groups wherein only the alkyl portionforms the linkage between the

moiety and the

moiety and the alkyl portion has aryl portions pending therefrom, suchas

and the like, or (iv) an alkylarylene group (including unsubstituted andsubstituted alkylarylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl portion and thealkyl portion of the alkylarylene group, provided that no oxygen atomcreates a

linkage), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 20 carbon atoms, in yet anotherembodiment with no more than about 7 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, including (a) alkylarylene groups wherein both the aryl and thealkyl portions form the linkage between the

moiety and the

moiety, such as

and the like, and (b) alkylarylene groups wherein only the aryl portionforms the linkage between the

moiety and the

moiety and the aryl portion has alkyl portions pending therefrom, suchas

and the like, wherein the substituents on the substituted alkylene,arylene, arylalkylene, or alkylarylene groups can be hydroxy groups,halogen atoms, amine groups, imine groups, ammonium groups, cyanogroups, pyridine groups, pyridinium groups, aldehyde groups, ketonegroups, ester groups, amide groups, carbonyl groups, thiocarbonylgroups, sulfate groups, sulfonate groups, sulfonic acid groups, sulfidegroups, sulfoxide groups, phosphine groups, phosphonium groups,phosphate groups, nitrile groups, mercapto groups, nitro groups, nitrosogroups, sulfone groups, acyl groups, acid anhydride groups, azidegroups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring,X is —O— or —NR₃— wherein R₃ is (i) a hydrogen atom, (ii) an alkyl group(including linear, branched, saturated, unsaturated, cyclic,substituted, and unsubstituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the alkyl group), in one embodimentwith at least about 1 carbon atom, and in one embodiment with no morethan about 60 carbon atoms, in another embodiment with no more thanabout 55 carbon atoms, and in yet another embodiment with no more thanabout 50 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (iii) an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the aryl group), in one embodiment with at least about5 carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 60 carbon atoms, inanother embodiment with no more than about 55 carbon atoms, and in yetanother embodiment with no more than about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iv) an arylalkylgroup (including substituted and unsubstituted arylalkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either thearyl or the alkyl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 60 carbon atoms, in another embodiment with no more than about 55carbon atoms, and in yet another embodiment with no more than about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as benzyl or the like, or (v) an alkylaryl group(including substituted and unsubstituted alkylaryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either the alkyl or thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 60 carbonatoms, in another embodiment with no more than about 55 carbon atoms,and in yet another embodiment with no more than about 50 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas tolyl or the like, and R₂ is (i) a hydrogen atom, (ii) an alkyl group(including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the alkyl group), in one embodimentwith at least about 1 carbon atom, in another embodiment with at leastabout 2 carbon atoms, in another embodiment with at least about 3 carbonatoms, in yet another embodiment with at least about 4 carbon atoms, instill another embodiment with at least about 5 carbon atoms, in anotherembodiment with at least about 6 carbon atoms, in yet another embodimentwith at least about 7 carbon atoms, in still another embodiment with atleast about 8 carbon atoms, in another embodiment with at least about 9carbon atoms, in yet another embodiment with at least about 10 carbonatoms, in still another embodiment with at least about 11 carbon atoms,in another embodiment with at least about 12 carbon atoms, in yetanother embodiment with at least about 13 carbon atoms, in still anotherembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 15 carbon atoms, in yet another embodiment with atleast about 16 carbon atoms, in still another embodiment with at leastabout 17 carbon atoms, in another embodiment with at least about 18carbon atoms, in yet another embodiment with at least about 19 carbonatoms, in still another embodiment with at least about 20 carbon atoms,in another embodiment with at least about 21 carbon atoms, in yetanother embodiment with at least about 22 carbon atoms, in still anotherembodiment with at least about 23 carbon atoms, in another embodimentwith at least about 24 carbon atoms, in yet another embodiment with atleast about 25 carbon atoms, in still another embodiment with at leastabout 26 carbon atoms, in another embodiment with at least about 27carbon atoms, in yet another embodiment with at least about 28 carbonatoms, in still another embodiment with at least about 29 carbon atoms,in another embodiment with at least about 30 carbon atoms, in yetanother embodiment with at least about 31 carbon atoms, in still anotherembodiment with at least about 32 carbon atoms, in another embodimentwith at least about 33 carbon atoms, in yet another embodiment with atleast about 34 carbon atoms, in still another embodiment with at leastabout 35 carbon atoms, in another embodiment with at least about 36carbon atoms, in yet another embodiment with at least about 37 carbonatoms, in still another embodiment with at least about 38 carbon atoms,in another embodiment with at least about 39 carbon atoms, in yetanother embodiment with at least about 40 carbon atoms, in still anotherembodiment with at least about 41 carbon atoms, in another embodimentwith at least about 42 carbon atoms, in yet another embodiment with atleast about 43 carbon atoms, in still another embodiment with at leastabout 44 carbon atoms, in another embodiment with at least about 45carbon atoms, in yet another embodiment with at least about 46 carbonatoms, in still another embodiment with at least about 47 carbon atoms,in another embodiment with at least about 48 carbon atoms, in yetanother embodiment with at least about 49 carbon atoms, and in stillanother embodiment with at least about 50 carbon atoms, and in oneembodiment with no more than about 100 carbon atoms, in anotherembodiment with no more than about 70 carbon atoms, in yet anotherembodiment with no more than about 60 carbon atoms, in still anotherembodiment with no more than about 55 carbon atoms, and in yet stillanother embodiment with no more than about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iii) an arylgroup (including unsubstituted and substituted aryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the aryl group), in oneembodiment with at least about 5 carbon atoms, in another embodimentwith at least about 6 carbon atoms, in yet another embodiment with atleast about 7 carbon atoms, in still another embodiment with at leastabout 8 carbon atoms, in another embodiment with at least about 9 carbonatoms, in yet another embodiment with at least about 10 carbon atoms, instill another embodiment with at least about 11 carbon atoms, in anotherembodiment with at least about 12 carbon atoms, in yet anotherembodiment with at least about 13 carbon atoms, in still anotherembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 15 carbon atoms, in yet another embodiment with atleast about 16 carbon atoms, in still another embodiment with at leastabout 17 carbon atoms, in another embodiment with at least about 18carbon atoms, in yet another embodiment with at least about 19 carbonatoms, in still another embodiment with at least about 20 carbon atoms,in another embodiment with at least about 21 carbon atoms, in yetanother embodiment with at least about 22 carbon atoms, in still anotherembodiment with at least about 23 carbon atoms, in another embodimentwith at least about 24 carbon atoms, in yet another embodiment with atleast about 25 carbon atoms, in still another embodiment with at leastabout 26 carbon atoms, in another embodiment with at least about 27carbon atoms, in yet another embodiment with at least about 28 carbonatoms, in still another embodiment with at least about 29 carbon atoms,in another embodiment with at least about 30 carbon atoms, in yetanother embodiment with at least about 31 carbon atoms, in still anotherembodiment with at least about 32 carbon atoms, in another embodimentwith at least about 33 carbon atoms, in yet another embodiment with atleast about 34 carbon atoms, in still another embodiment with at leastabout 35 carbon atoms, in another embodiment with at least about 36carbon atoms, in yet another embodiment with at least about 37 carbonatoms, in still another embodiment with at least about 38 carbon atoms,in another embodiment with at least about 39 carbon atoms, in yetanother embodiment with at least about 40 carbon atoms, in still anotherembodiment with at least about 41 carbon atoms, in another embodimentwith at least about 42 carbon atoms, in yet another embodiment with atleast about 43 carbon atoms, in still another embodiment with at leastabout 44 carbon atoms, in another embodiment with at least about 45carbon atoms, in yet another embodiment with at least about 46 carbonatoms, in still another embodiment with at least about 47 carbon atoms,in another embodiment with at least about 48 carbon atoms, in yetanother embodiment with at least about 49 carbon atoms, and in stillanother embodiment with at least about 50 carbon atoms, and in oneembodiment with no more than about 100 carbon atoms, in anotherembodiment with no more than about 70 carbon atoms, in yet anotherembodiment with no more than about 60 carbon atoms, in still anotherembodiment with no more than about 55 carbon atoms, and in yet stillanother embodiment with no more than about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (iv) an arylalkylgroup (including unsubstituted and substituted arylalkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either orboth of the alkyl portion and the aryl portion of the arylalkyl group),in one embodiment with at least about 6 carbon atoms, in anotherembodiment with at least about 7 carbon atoms, in yet another embodimentwith at least about 8 carbon atoms, in another embodiment with at leastabout 9 carbon atoms, in yet another embodiment with at least about 10carbon atoms, in still another embodiment with at least about 11 carbonatoms, in another embodiment with at least about 12 carbon atoms, in yetanother embodiment with at least about 13 carbon atoms, in still anotherembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 15 carbon atoms, in yet another embodiment with atleast about 16 carbon atoms, in still another embodiment with at leastabout 17 carbon atoms, in another embodiment with at least about 18carbon atoms, in yet another embodiment with at least about 19 carbonatoms, in still another embodiment with at least about 20 carbon atoms,in another embodiment with at least about 21 carbon atoms, in yetanother embodiment with at least about 22 carbon atoms, in anotherembodiment with at least about 23 carbon atoms, in yet anotherembodiment with at least about 24 carbon atoms, in still anotherembodiment with at least about 25 carbon atoms, in another embodimentwith at least about 26 carbon atoms, in yet another embodiment with atleast about 27 carbon atoms, in still another embodiment with at leastabout 28 carbon atoms, in another embodiment with at least about 29carbon atoms, in yet another embodiment with at least about 30 carbonatoms, in still another embodiment with at least about 31 carbon atoms,in another embodiment with at least about 32 carbon atoms, in yetanother embodiment with at least about 33 carbon atoms, in still anotherembodiment with at least about 34 carbon atoms, in another embodimentwith at least about 35 carbon atoms, in yet another embodiment with atleast about 36 carbon atoms, in still another embodiment with at leastabout 37 carbon atoms, in another embodiment with at least about 38carbon atoms, in yet another embodiment with at least about 39 carbonatoms, in still another embodiment with at least about 40 carbon atoms,in another embodiment with at least about 41 carbon atoms, in yetanother embodiment with at least about 42 carbon atoms, in still anotherembodiment with at least about 43 carbon atoms, in another embodimentwith at least about 44 carbon atoms, in yet another embodiment with atleast about 45 carbon atoms, in still another embodiment with at leastabout 46 carbon atoms, in another embodiment with at least about 47carbon atoms, in yet another embodiment with at least about 48 carbonatoms, in still another embodiment with at least about 49 carbon atoms,and in yet still another embodiment with at least about 50 carbon atoms,and in one embodiment with no more than about 100 carbon atoms, inanother embodiment with no more than about 70 carbon atoms, in yetanother embodiment with no more than about 60 carbon atoms, in stillanother embodiment with no more than about 55 carbon atoms, and in yetstill another embodiment with no more than about 50 carbon atoms,although the number of carbon atoms can be outside of these ranges, or(v) an alkylaryl group (including unsubstituted and substitutedalkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in either or both of the alkyl portion and the aryl portion ofthe alkylaryl group), in one embodiment with at least about 6 carbonatoms, in another embodiment with at least about 7 carbon atoms, in yetanother embodiment with at least about 8 carbon atoms, in anotherembodiment with at least about 9 carbon atoms, in yet another embodimentwith at least about 10 carbon atoms, in still another embodiment with atleast about 11 carbon atoms, in another embodiment with at least about12 carbon atoms, in yet another embodiment with at least about 13 carbonatoms, in still another embodiment with at least about 14 carbon atoms,in another embodiment with at least about 15 carbon atoms, in yetanother embodiment with at least about 16 carbon atoms, in still anotherembodiment with at least about 17 carbon atoms, in another embodimentwith at least about 18 carbon atoms, in yet another embodiment with atleast about 19 carbon atoms, in still another embodiment with at leastabout 20 carbon atoms, in another embodiment with at least about 21carbon atoms, in yet another embodiment with at least about 22 carbonatoms, in another embodiment with at least about 23 carbon atoms, in yetanother embodiment with at least about 24 carbon atoms, in still anotherembodiment with at least about 25 carbon atoms, in another embodimentwith at least about 26 carbon atoms, in yet another embodiment with atleast about 27 carbon atoms, in still another embodiment with at leastabout 28 carbon atoms, in another embodiment with at least about 29carbon atoms, in yet another embodiment with at least about 30 carbonatoms, in still another embodiment with at least about 31 carbon atoms,in another embodiment with at least about 32 carbon atoms, in yetanother embodiment with at least about 33 carbon atoms, in still anotherembodiment with at least about 34 carbon atoms, in another embodimentwith at least about 35 carbon atoms, in yet another embodiment with atleast about 36 carbon atoms, in still another embodiment with at leastabout 37 carbon atoms, in another embodiment with at least about 38carbon atoms, in yet another embodiment with at least about 39 carbonatoms, in still another embodiment with at least about 40 carbon atoms,in another embodiment with at least about 41 carbon atoms, in yetanother embodiment with at least about 42 carbon atoms, in still anotherembodiment with at least about 43 carbon atoms, in another embodimentwith at least about 44 carbon atoms, in yet another embodiment with atleast about 45 carbon atoms, in still another embodiment with at leastabout 46 carbon atoms, in another embodiment with at least about 47carbon atoms, in yet another embodiment with at least about 48 carbonatoms, in still another embodiment with at least about 49 carbon atoms,and in yet still another embodiment with at least about 50 carbon atoms,and in one embodiment with no more than about 100 carbon atoms, inanother embodiment with no more than about 70 carbon atoms, in yetanother embodiment with no more than about 60 carbon atoms, in stillanother embodiment with no more than about 55 carbon atoms, and in yetstill another embodiment with no more than about 50 carbon atoms,although the number of carbon atoms can be outside of these ranges,wherein the substituents on the substituted alkyl, aryl, arylalkyl, andalkylaryl groups can be (but are not limited to) hydroxy groups, halogenatoms, amine groups, imine groups, ammonium groups, cyano groups,pyridine groups, pyridinium groups, ether groups, aldehyde groups,ketone groups, ester groups, amide groups, carbonyl groups, thiocarbonylgroups, sulfate groups, sulfonate groups, sulfonic acid groups, sulfidegroups, sulfoxide groups, phosphine groups, phosphonium groups,phosphate groups, nitrile groups, mercapto groups, nitro groups, nitrosogroups, sulfone groups, acyl groups, acid anhydride groups, azidegroups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring.Since hetero atoms such as oxygen can be present in the alkyl, aryl,alkylene, arylene, and the like groups, these groups also encompassgroups such as alkoxy, aryloxy, alkyleneoxy, polyalkyleneoxy, and thelike.

In one specific embodiment, at least one of R₂ and R₃ is other thanhydrogen and the total number of carbon atoms in R₂+R₃ is at least about8, in another specific embodiment at least about 12, and in yet anotherspecific embodiment at least about 18, and in one specific embodiment,the total number of carbon atoms in R₂+R₃ is no more than about 100, inanother specific embodiment no more than about 60, and in yet anotherspecific embodiment no more than about 50, although the total number ofcarbon atoms in R₂+R₃ can be outside of these ranges.

The above formula encompasses monomeric materials. In addition, theabove formula encompasses dimeric materials containing two moieties ofthe formula

such as dimeric materials of the formula

wherein X′ has the same definition as X and can be either the same as ordifferent from X, Y′ has the same definition as Y and can be either thesame as or different from Y, R₁′ has the same definition as R₁ and canbe either the same as or different from R₁, and n′ is an integer of 0,1, 2, 3, or 4 and can be either the same as or different from n. R₂ inthis embodiment can be (i) an alkylene group (including linear,branched, saturated, unsaturated, cyclic, substituted, and unsubstitutedalkylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the alkylene group), in one embodiment with at least about 1carbon atom, and in one embodiment with no more than about 50 carbonatoms, although the number of carbon atoms can be outside of theseranges, (ii) an arylene group (including unsubstituted and substitutedarylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the arylene group), in one embodiment with at least about 5carbon atoms, and in another embodiment with at least about 6 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas phenyl or the like, (iii) an arylalkylene group (includingunsubstituted and substituted arylalkylene groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either or both of the arylportion and the alkyl portion of the arylalkylene group), in oneembodiment with at least about 6 carbon atoms, and in another embodimentwith at least about 7 carbon atoms, and in one embodiment with no morethan about 50 carbon atoms, although the number of carbon atoms can beoutside of these ranges, such as benzyl, phenylethyl, and the like, or(iv) an alkylarylene group (including unsubstituted and substitutedalkylarylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in either or both of the aryl portion and the alkyl portion ofthe alkylarylene group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as tolyl orthe like, wherein the substituents on the substituted alkylene, arylene,arylalkylene, or alkylarylene groups can be (but are not limited to)hydroxy groups, halogen atoms, amine groups, imine groups, ammoniumgroups, cyano groups, pyridine groups, pyridinium groups, ether groups,aldehyde groups, ketone groups, ester groups, amide groups, carbonylgroups, thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonicacid groups, sulfide groups, sulfoxide groups, phosphine groups,phosphonium groups, phosphate groups, nitrile groups, mercapto groups,nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, azo groups, cyanato groups, isocyanatogroups, thiocyanato groups, isothiocyanato groups, carboxylate groups,carboxylic acid groups, urethane groups, urea groups, mixtures thereof,and the like, wherein two or more substituents can be joined together toform a ring. Since hetero atoms such as oxygen can be present in thealkyl, aryl, alkylene, arylene, and the like groups, these groups alsoencompass groups such as alkoxy, aryloxy, alkyleneoxy, polyalkyleneoxy,and the like.

Similarly, the above formula encompasses trimeric, tetrameric, andhigher moieties as well as oligomeric materials and polymeric materials,said materials containing three or more moieties of the formula

wherein each X, Y, R₁, and n, independently of the others, has thedefinitions for X, Y, R₁, and n set forth hereinabove and can be eitherthe same as or different from one another, said moieties being linked bya central atom or group of atoms or bonded to a polymeric chain. Thesematerials can be made by processes analogous to those illustrated hereinfor the monomeric and dimeric compounds of the present invention.

The colorant compounds disclosed herein can be prepared by any desiredor effective method.

For example, an acid-substituted precursor compound can be prepared byreacting (1) leucoquinizarin and, optionally, quinizarin, (2) a compoundof the formula NHR₃-φ-R₁—COOH wherein φ represents a benzene ring andwherein R₁ and R₃ are as defined hereinabove, (3) boric acid, and (4) anoptional solvent, followed by heating this reaction mixture to effectcondensation as follows (illustrated for an embodiment wherein thecompound of the formula NHR₃-φ-R₁—COOH is para-aminophenylacetic acid):

While quinizarin is shown above as the starting material, the presenceof leucoquinizarin, which is the reduced form of quinizarin, is helpfulfor condensing with the acid-substituted amine. The reaction between theamine and the leucoquinizarin further reduces some of the quinizarinpresent in the reaction mixture to leucoquinizarin, thereby rendering itcapable of reacting with more of the amine and furthering the reactionto completion. If desired, the reaction can be carried out solely withleucoquinizarin and with no quinizarin, although for economical purposessuch a procedure is often not desirable. In addition, instead of addingleucoquinizarin to a reaction mixture of quinizarin and theacid-substituted amine, leucoquinizarin can be generated in situ bypreparing a reaction mixture of quinizarin and the acid-substitutedamine and adding to the reaction mixture a reducing agent, as disclosedin, for example, Waring and Hallas, The Chemistry and Application ofDyes, ISBN 0-306-43278-1, Plenum Publishing Co. (New York 1990), thedisclosure of which is totally incorporated herein by reference.

The quinizarin and the leucoquinizarin are present in any desired oreffective relative amounts, in one embodiment at least about 5 moles ofleucoquinizarin per every 95 moles of quinizarin, in another embodimentat least about 2 moles of leucoquinizarin per every 3 moles ofquinizarin, and in yet another embodiment at least about 1 mole ofleucoquinizarin per every 1 mole of quinizarin, and in one embodiment upto 100 percent leucoquinizarin and no quinizarin, although the relativeamounts of quinizarin and leucoquinizarin can be outside of theseranges.

The compound of the formula NHR₃—OR₁—COOH (hereinafter also referred toas the acid-substituted aminobenzene) is present in any desired oreffective amount, in one embodiment at least about 0.95 mole ofacid-substituted aminobenzene per every one mole of (quinizarin plusleucoquinizarin), and in another embodiment at least about 1 mole ofacid-substituted aminobenzene per every one mole of (quinizarin plusleucoquinizarin), and in one embodiment no more than about 1.05 moles ofacid-substituted aminobenzene per every one mole of (quinizarin plusleucoquinizarin), and in another embodiment no more than about 1 mole ofacid-substituted aminobenzene per every one mole of (quinizarin plusleucoquinizarin), although the amount of acid-substituted aminobenzenecan be outside of these ranges.

The boric acid, which functions as a catalyst in the reaction betweenthe acid-substituted aminobenzene and the leucoquinizarin, is present inany desired or effective amount, in one embodiment about 1 mole of boricacid per every one mole of (quinizarin plus leucoquinizarin), althoughthe amount of boric acid can be higher or lower than this amount.

When the optional solvent is present, any desired or effective solventcan be used. Examples of suitable solvents include toluene, xylene,chlorobenzene, and the like, as well as mixtures thereof. The reactantsare present in the solvent in any desired or effective amount, in oneembodiment at least about 25 grams of acid-substituted aminobenzene perevery one liter of solvent, in another embodiment at least about 50grams of acid-substituted aminobenzene per every one liter of solvent,and in another embodiment at least about 100 grams of acid-substitutedaminobenzene per every one liter of solvent, and in one embodiment nomore than about 500 grams of acid-substituted aminobenzene per every oneliter of solvent, in another embodiment no more than about 250 grams ofacid-substituted aminobenzene per every one liter of solvent, and in yetanother embodiment no more than about 125 grams of acid-substitutedaminobenzene per every one liter of solvent, although the amount ofsolvent can be outside of these ranges.

The reaction mixture containing (1) leucoquinizarin and, optionally,quinizarin, (2) a compound of the formula NHR₃-φ-R₁—COOH, (3) boricacid, and (4) an optional solvent is heated to any desirable oreffective temperature to effect the condensation reaction, typically thereflux temperature of the selected solvent when a solvent is used, inone embodiment at least about 50° C., in another embodiment at leastabout 60° C., and in yet another embodiment at least about 75° C., andin one embodiment no more than about 150° C., in another embodiment nomore than about 120° C., and in yet another embodiment no more thanabout 80° C., although the temperature can be outside of these ranges.

The reaction mixture containing (1) leucoquinizarin and, optionally,quinizarin, (2) a compound of the formula NHR₃-φ-R₁—COOH, (3) boricacid, and (4) an optional solvent is heated for any desirable oreffective period of time to effect the condensation reaction, in oneembodiment at least about 3 hours, and in another embodiment at leastabout 4 hours, and in one embodiment no more than about 24 hours,although the heating time can be outside of these ranges.

Upon completion of the reaction, the acid-substituted precursor isformed as a solid and can be recovered by cooling and filtering thereaction mixture.

The acid-substituted precursor compound is converted to the colorant byan esterification or amidification reaction and a bromination reaction.The acid-substituted precursor compound can be subjected to anesterification or amidification reaction, followed by subjecting theesterified compound to a bromination reaction. Alternatively, theacid-substituted precursor compound can be subjected to a brominationreaction, followed by subjecting the brominated compound to anesterification or amidification reaction. Both possibilities arediscussed herein.

The acid-substituted precursor or brominated acid-substituted precursorcan be esterified to form an ester-substituted compound and its salt ora brominated ester-substituted colorant and its salt by admixing theprecursor with an alcohol of the formula R₂—OH, an optional solvent, andan optional esterification catalyst and heating, as follows (illustratedfor an embodiment wherein Y is a hydrogen atom, n is 0, and X is —O—):

The acid-substituted precursor or brominated acid-substituted precursorand the alcohol are present in any desired or effective relativeamounts, in one embodiment at least about 1 mole of alcohol per everyone mole of acid-substituted precursor or brominated acid-substitutedprecursor, in another embodiment at least about 1.05 moles of alcoholper every one mole of acid-substituted precursor or brominatedacid-substituted precursor, and in yet another embodiment at least about1.1 moles of alcohol per every one mole of acid-substituted precursor orbrominated acid-substituted precursor, and in one embodiment no morethan about 2 moles of alcohol per every one mole of acid-substitutedprecursor or brominated acid-substituted precursor, in anotherembodiment no more than about 1.5 moles of alcohol per every one mole ofacid-substituted precursor or brominated acid-substituted precursor, andin yet another embodiment no more than about 1.25 moles of alcohol perevery one mole of acid-substituted precursor or brominatedacid-substituted precursor, although the relative amounts ofacid-substituted precursor or brominated acid-substituted precursor andalcohol can be outside of these ranges.

When the optional esterification catalyst is present, any desired oreffective esterification catalyst can be used, such as para-toluenesulfonic acid, dibutyl tin dilaurate, or the like, as well as mixturesthereof. The esterification catalyst is present in any desired oreffective amount, in one embodiment at least about 0.05 mole ofesterification catalyst per every one mole of alcohol, and in oneembodiment no more than about 0.5 mole of esterification catalyst permole of alcohol, although the amount of esterification catalyst can beoutside of these ranges.

When present, any desired or effective solvent can be used. Examples ofsuitable solvents include xylene, toluene, benzene, chlorobenzene,nitrobenzene, dichlorobenzene, and the like, as well as mixturesthereof. When the optional solvent is used, the reactants are present inthe solvent in any desired or effective amount, in one embodiment atleast about 25 grams of alcohol per every one liter of solvent, inanother embodiment at least about 50 grams of alcohol per every oneliter of solvent, and in yet another embodiment at least about 100 gramsof alcohol per every one liter of solvent, and in one embodiment no morethan about 200 grams of alcohol per every one liter of solvent, inanother embodiment no more than about 150 grams of alcohol per every oneliter of solvent, and in yet another embodiment no more than about 100grams of alcohol per every one liter of solvent, although the amount ofsolvent can be outside of these ranges.

The reaction mixture containing the alcohol, the acid-substitutedprecursor or brominated acid-substituted precursor, the optionalsolvent, and the optional esterification catalyst is heated to anydesirable or effective temperature, typically the reflux temperature ofthe selected solvent, in one embodiment at least about 100° C., and inone embodiment no more than about 130° C., although the temperature canbe outside of these ranges.

The reaction mixture containing the alcohol, the acid-substitutedprecursor or brominated acid-substituted precursor, the optionalsolvent, and the optional esterification catalyst is heated for anydesirable or effective period of time, in one embodiment at least about2 hours, in another embodiment at least about 24 hours, and in oneembodiment no more than about 72 hours, and in another embodiment nomore than about 48 hours, although the heating time can be outside ofthese ranges.

The esterified compound or the brominated esterified colorant can berecovered from the reaction mixture as a solid by filtration, followedby washing and drying. If desired, purification can be carried out byfiltration, redissolution in the solvent, heating, cooling,precipitating the colorant from the solution, filtering, washing thecolorant with a solvent such as methanol, ethanol, or the like, andrepeating this cycle until thin layer chromatography of the collectedsolid indicates that there is no detectable unreacted reactant presentin the solid.

The acid-substituted precursor or brominated acid-substituted precursorcan be amidified to form an amide-substituted compound and its salt or abrominated amide-substituted colorant and its salt by admixing theprecursor with a primary or secondary amine of the formula NHR₂R₃, anoptional solvent, and an optional amidification catalyst and heating, asfollows (illustrated for an embodiment wherein Y is a hydrogen atom, nis 0, R₃ is a hydrogen atom, and X is —NH—):

The acid-substituted precursor or brominated acid-substituted precursorand the amine are present in any desired or effective relative amounts,in one embodiment at least about 1 mole of amine per every one mole ofacid-substituted precursor or brominated acid-substituted precursor, inanother embodiment at least about 1.05 moles of amine per every one moleof acid-substituted precursor or brominated acid-substituted precursor,and in yet another embodiment at least about 1.1 moles of amine perevery one mole of acid-substituted precursor or brominatedacid-substituted precursor, and in one embodiment no more than about 2moles of amine per every one mole of acid-substituted precursor orbrominated acid-substituted precursor, in another embodiment no morethan about 1.5 moles of amine per every one mole of acid-substitutedprecursor or brominated acid-substituted precursor, and in yet anotherembodiment no more than about 1.25 moles of amine per every one mole ofacid-substituted precursor or brominated acid-substituted precursor,although the relative amounts of acid-substituted precursor orbrominated acid-substituted precursor and amine can be outside of theseranges.

When the optional amidification catalyst is present, any desired oreffective amidification catalyst can be used, such as phosphoric acid orthe like. The amidification catalyst is present in any desired oreffective amount, in one embodiment at least about 0.05 mole ofamidification catalyst per every one mole of amine, and in oneembodiment no more than about 0.5 mole of amidification catalyst permole of amine, although the amount of amidification catalyst can beoutside of these ranges.

When present, any desired or effective solvent can be used. Examples ofsuitable solvents include xylene, toluene, benzene, chlorobenzene,nitrobenzene, dichlorobenzene, and the like, as well as mixturesthereof. When the optional solvent is used, the reactants are present inthe solvent in any desired or effective amount, in one embodiment atleast about 25 grams of amine per every one liter of solvent, in anotherembodiment at least about 50 grams of amine per every one liter ofsolvent, and in yet another embodiment at least about 100 grams of amineper every one liter of solvent, and in one embodiment no more than about200 grams of amine per every one liter of solvent, in another embodimentno more than about 150 grams of amine per every one liter of solvent,and in yet another embodiment no more than about 100 grams of amine perevery one liter of solvent, although the amount of solvent can beoutside of these ranges.

The reaction mixture containing the amine, the acid-substitutedprecursor or brominated acid-substituted precursor, the optionalsolvent, and the optional amidification catalyst is heated to anydesirable or effective temperature, typically the reflux temperature ofthe selected solvent, in one embodiment at least about 100° C., and inone embodiment no more than about 200° C., although the temperature canbe outside of these ranges.

The reaction mixture containing the amine, the acid-substitutedprecursor or brominated acid-substituted precursor, the optionalsolvent, and the optional amidification catalyst is heated for anydesirable or effective period of time, in one embodiment at least about2 hours, in another embodiment at least about 24 hours, and in oneembodiment no more than about 72 hours, and in another embodiment nomore than about 48 hours, although the heating time can be outside ofthese ranges.

The amidified compound or the brominated amidified colorant can berecovered from the reaction mixture as a solid by filtration, followedby washing and drying. If desired, purification can be carried out byfiltration, redissolution in the solvent, heating, cooling,precipitating the colorant from the solution, filtering, washing thecolorant with a solvent such as methanol, ethanol, or the like, andrepeating this cycle until thin layer chromatography of the collectedsolid indicates that there is no detectable unreacted reactant presentin the solid.

The acid-substituted precursor, unbrominated esterified compound, orunbrominated amidified compound can be brominated to form a brominatedacid, ester, or amide substituted colorant and its salt by admixing itwith bromine and an optional solvent, followed by quenching with water,as follows (illustrated for an embodiment wherein the acid-substitutedprecursor was prepared from para-aminophenylacetic acid and wherein thebrominated product has Y being a hydrogen atom, n=2, and the two bromineatoms in the ortho positions adjacent to the nitrogen atom):

The mixture of products contains both an amine compound and the HBr saltthereof.

Bromine (Br₂) can be provided by any desired or effective method, suchas by adding elemental bromine, or by generating Br₂ in situ in thereaction mixture by the addition of a combination of a bromide salt anda bromate salt, as disclosed in, for example, Kirk-Othmer Encyclopediaof Chemical Technology, Vol. 4, 4th Edition, ISBN 0-471-52672-X JohnWiley & Sons, Inc. (New York 1992), the disclosure of which is totallyincorporated herein by reference, or the like.

The acid-substituted precursor, unbrominated esterified compound, orunbrominated amidified compound and the bromine are present in anydesired or effective relative amounts, in one embodiment at least about2 moles of Br₂ per every one mole of acid-substituted precursor,unbrominated esterified compound, or unbrominated amidified compound, inanother embodiment at least about 2.5 moles of Br₂ per every one mole ofacid-substituted precursor, unbrominated esterified compound, orunbrominated amidified compound, and in yet another embodiment at leastabout 3 moles of Br₂ per every one mole of acid-substituted precursor,unbrominated esterified compound, or unbrominated amidified compound,and in one embodiment no more than about 4 moles of Br₂ per every onemole of acid-substituted precursor, unbrominated esterified compound, orunbrominated amidified compound, in another embodiment no more thanabout 3.5 moles of Br₂ per every one mole of acid-substituted precursor,unbrominated esterified compound, or unbrominated amidified compound,and in yet another embodiment no more than about 3.25 moles of Br₂ perevery one mole of acid-substituted precursor, unbrominated esterifiedcompound, or unbrominated amidified compound, although the amount ofbromine can be outside of these ranges. Higher amounts of bromine leadto higher degrees of substitution with bromine atoms. Greater amounts ofbromine and/or higher reaction temperatures are selected when it isdesired to place a bromine atom in the Y position.

Examples of suitable optional solvents include acetic acid, propionicacid, formic acid, butyric acid, dimethyl formamide, dimethyl sulfoxide,hexamethyl phosphorus triamide (HMPA), tetrahydrofuran, or the like, aswell as mixtures thereof. When present, the optional solvent is presentin any desired or effective amount, in one embodiment at least about 25grams of acid-substituted precursor, unbrominated esterified compound,or unbrominated amidified compound per every one liter of solvent, andin another embodiment at least about 100 grams of acid-substitutedprecursor, unbrominated esterified compound, or unbrominated amidifiedcompound per every one liter of solvent, and in one embodiment no morethan about 200 grams of acid-substituted precursor, unbrominatedesterified compound, or unbrominated amidified compound per every oneliter of solvent, although the amount of solvent can be outside of theseranges.

The reaction mixture containing the acid-substituted precursor,unbrominated esterified compound, or unbrominated amidified compound,the bromine, and the optional solvent generally can be initially heatedto a temperature of about 30° C. to about 40° C. The reaction of theacid-substituted precursor, unbrominated esterified compound, orunbrominated amidified compound with the bromine tends to be exothermic,and the reaction mixture is generally maintained at a desirabletemperature by controlling the rate of addition of bromine as well as byany desired external source, such as a heating mantle or the like. Thereaction mixture containing the acid-substituted precursor, unbrominatedesterified compound, or unbrominated amidified compound, the bromine,and the solvent is maintained any desirable or effective temperature, inone embodiment at least about 25° C., and in another embodiment at leastabout 50° C., and in one embodiment no more than about 100° C., and inanother embodiment no more than about 60° C., although the temperaturecan be outside of these ranges.

The reaction between the acid-substituted precursor, unbrominatedesterified compound, or unbrominated amidified compound and the bromineis allowed to proceed for any desirable or effective period of time, inone embodiment at least about 5 hours, and in one embodiment no morethan about 24 hours, although the reaction time can be outside of theseranges.

Subsequent to completion of the bromination reaction, the reactionmixture can be poured into water to quench the reaction. Any desired oreffective amount of water can be used—in one embodiment at least about1.5 times as much water by volume as the volume of the reaction mixture,in another embodiment at least about 2 times as much water by volume asthe volume of the reaction mixture, in yet another embodiment at leastabout 2 times as much water by volume as the volume of the reactionmixture, and in still another embodiment at least about 3 times as muchwater by volume as the volume of the reaction mixture, although theamount of water can be outside of these ranges.

The mixture of the brominated compound and its salt can be recoveredfrom the reaction mixture as a solid by filtration, washed, and dried.

Phase change inks as disclosed herein contain a phase change carriersystem or composition. The phase change carrier composition is typicallydesigned for use in either a direct printing mode or an indirect oroffset printing transfer system.

In the direct printing mode, the phase change carrier composition in oneembodiment contains one or more materials that enable the phase changeink (1) to be applied in a thin film of uniform thickness on the finalrecording substrate (such as paper, transparency material, and the like)when cooled to ambient temperature after printing directly to therecording substrate, (2) to be ductile while retaining sufficientflexibility so that the applied image on the substrate will not fractureupon bending, and (3) to possess a high degree of lightness, chroma,transparency, and thermal stability.

In an offset printing transfer or indirect printing mode, the phasechange carrier composition in one embodiment exhibits not only thecharacteristics desirable for direct printing mode inks, but alsocertain fluidic and mechanical properties desirable for use in such asystem, as described in, for example, U.S. Pat. No. 5,389,958 thedisclosure of which is totally incorporated herein by reference.

Any desired or effective carrier composition can be used. Examples ofsuitable ink carrier materials include fatty amides, such as monoamides,tetra-amides, mixtures thereof, and the like. Specific examples ofsuitable fatty amide ink carrier materials include stearyl stearamide, adimer acid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and stearic acid, a dimer acid based tetra-amide thatis the reaction product of dimer acid, ethylene diamine, and acarboxylic acid having at least about 36 carbon atoms, and the like, aswell as mixtures thereof. When the fatty amide ink carrier is a dimeracid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and a carboxylic acid having at least about 36 carbonatoms, the carboxylic acid is of the general formula

wherein R is an alkyl group, including linear, branched, saturated,unsaturated, and cyclic alkyl groups, said alkyl group in one embodimenthaving at least about 36 carbon atoms, in another embodiment having atleast about 40 carbon atoms, said alkyl group in one embodiment havingno more than about 200 carbon atoms, in another embodiment having nomore than about 150 carbon atoms, and in yet another embodiment havingno more than about 100 carbon atoms, although the number of carbon atomscan be outside of these ranges. Carboxylic acids of this formula arecommercially available from, for example, Baker Petrolite, Tulsa, Okla.,and can also be prepared as described in Example 1 of U.S. Pat. No.6,174,937, the disclosure of which is totally incorporated herein byreference. Further information on fatty amide carrier materials isdisclosed in, for example, U.S. Pat. No. 4,889,560, U.S. Pat. No.4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No. 4,830,671, U.S. Pat.No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,597,856, U.S.Pat. No. 6,174,937, and British Patent GB 2 238 792, the disclosures ofeach of which are totally incorporated herein by reference.

Also suitable as phase change ink carrier materials areisocyanate-derived resins and waxes, such as urethane isocyanate-derivedmaterials, urea isocyanate-derived materials, urethane/ureaisocyanate-derived materials, mixtures thereof, and the like. Furtherinformation on isocyanate-derived carrier materials is disclosed in, forexample, U.S. Pat. No. 5,750,604, U.S. Pat. No. 5,780,528, U.S. Pat. No.5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat.No. 5,830,942, U.S. Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S.Pat. No. 6,309,453, British Patent GB 2 294 939, British Patent GB 2 305928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCTPublication WO 94/14902, PCT Publication WO 97/12003, PCT Publication WO97/13816, PCT Publication WO 96/14364, PCT Publication WO 97/33943, andPCT Publication WO 95/04760, the disclosures of each of which aretotally incorporated herein by reference.

Mixtures of fatty amide materials and isocyanate-derived materials canalso be employed as the ink carrier composition.

Additional suitable phase change ink carrier materials includeparaffins, microcrystalline waxes, polyethylene waxes, ester waxes,amide waxes, fatty acids, fatty alcohols, fatty amides and other waxymaterials, sulfonamide materials, resinous materials made from differentnatural sources (such as, for example, tall oil rosins and rosinesters), and many synthetic resins, oligomers, polymers and copolymers,such as ethylene/vinyl acetate copolymers, ethylene/acrylic acidcopolymers, ethylene/vinyl acetate/acrylic acid copolymers, copolymersof acrylic acid with polyamides, and the like, ionomers, and the like,as well as mixtures thereof. One or more of these materials can also beemployed in a mixture with a fatty amide material and/or anisocyanate-derived material.

In one specific embodiment, the phase change ink carrier comprises (a) apolyethylene wax, present in the ink in an amount in one embodiment ofat least about 25 percent by weight of the ink, in another embodiment ofat least about 30 percent by weight of the ink, and in yet anotherembodiment of at least about 37 percent by weight of the ink, and in oneembodiment of no more than about 60 percent by weight of the ink, inanother embodiment of no more than about 53 percent by weight of theink, and in yet another embodiment of no more than about 48 percent byweight of the ink, although the amount can be outside of these ranges;(b) a stearyl stearamide wax, present in the ink in an amount in oneembodiment of at least about 8 percent by weight of the ink, in anotherembodiment of at least about 10 percent by weight of the ink, and in yetanother embodiment of at least about 12 percent by weight of the ink,and in one embodiment of no more than about 32 percent by weight of theink, in another embodiment of no more than about 28 percent by weight ofthe ink, and in yet another embodiment of no more than about 25 percentby weight of the ink, although the amount can be outside of theseranges: (c) a dimer acid based tetra-amide that is the reaction productof dimer acid, ethylene diamine, and a long chain hydrocarbon havinggreater than thirty six carbon atoms and having a terminal carboxylicacid group, present in the ink in an amount in one embodiment of atleast about 10 percent by weight of the ink, in another embodiment of atleast about 13 percent by weight of the ink, and in yet anotherembodiment of at least about 16 percent by weight of the ink, and in oneembodiment of no more than about 32 percent by weight of the ink, inanother embodiment of no more than about 27 percent by weight of theink, and in yet another embodiment of no more than about 22 percent byweight of the ink, although the amount can be outside of these ranges;(d) a urethane resin derived from the reaction of two equivalents ofhydroabietyl alcohol and one equivalent of isophorone diisocyanate,present in the ink in an amount in one embodiment of at least about 6percent by weight of the ink, in another embodiment of at least about 8percent by weight of the ink, and in yet another embodiment of at leastabout 10 percent by weight of the ink, and in one embodiment of no morethan about 16 percent by weight of the ink, in another embodiment of nomore than about 14 percent by weight of the ink, and in yet anotherembodiment of no more than about 12 percent by weight of the ink,although the amount can be outside of these ranges; (e) a urethane resinthat is the adduct of three equivalents of stearyl isocyanate and aglycerol-based propoxylate alcohol, present in the ink in an amount inone embodiment of at least about 2 percent by weight of the ink, inanother embodiment of at least about 3 percent by weight of the ink, andin yet another embodiment of at least about 4.5 percent by weight of theink, and in one embodiment of no more than about 13 percent by weight ofthe ink, in another embodiment of no more than about 10 percent byweight of the ink, and in yet another embodiment of no more than about7.5 percent by weight of the ink, although the amount can be outside ofthese ranges; and (f) an antioxidant, present in the ink in an amount inone embodiment of at least about 0.01 percent by weight of the ink, inanother embodiment of at least about 0.05 percent by weight of the ink,and in yet another embodiment of at least about 0.1 percent by weight ofthe ink, and in one embodiment of no more than about 1 percent by weightof the ink, in another embodiment of no more than about 0.5 percent byweight of the ink, and in yet another embodiment of no more than about0.3 percent by weight of the ink, although the amount can be outside ofthese ranges.

The ink carrier is present in the phase change ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 50 percent byweight of the ink, and in yet another embodiment of at least about 90percent by weight of the ink, and in one embodiment of no more thanabout 99 percent by weight of the ink, in another embodiment of no morethan about 98 percent by weight of the ink, and in yet anotherembodiment of no more than about 95 percent by weight of the ink,although the amount can be outside of these ranges.

The phase change inks contain a colorant compound of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group, an arylene group, an arylalkylenegroup, or an alkylarylene group, provided that no oxygen atom creates a

linkage, X is —O— or —NR₃— wherein R₃ is a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, or an alkylaryl group, and R₂is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group. This colorant is present in the ink in anydesired or effective amount to obtain the desired color or hue, in oneembodiment of at least about 0.1 percent by weight of the ink, inanother embodiment of at least about 0.5 percent by weight of the ink,in yet another embodiment of at least about 1 percent by weight of theink, in still another embodiment of at least about 2 percent by weightof the ink, and in another embodiment of at least about 3 percent byweight of the ink, and in one embodiment of no more than about 20percent by weight of the ink, in another embodiment of no more thanabout 13 percent by weight of the ink, and in yet another embodiment ofno more than about 6 percent by weight of the ink, although the amountcan be outside of these ranges. The colorant as disclosed herein caneither be the sole colorant in the ink or can be present in combinationwith other colorants, such as dyes, pigments, mixtures thereof, and thelike.

The inks can also optionally contain an antioxidant. The optionalantioxidants of the ink compositions protect the images from oxidationand also protect the ink components from oxidation during the heatingportion of the ink preparation process. Specific examples of suitableantioxidants include NAUGUARD® 524, NAUGUARD® 76, and NAUGUARD® 512(commercially available from Uniroyal Chemical Company, Oxford, Conn.),IRGANOX® 1010 (commercially available from Ciba Geigy), and the like.When present, the optional antioxidant is present in the ink in anydesired or effective amount, in one embodiment of at least about 0.01percent by weight of the ink, in another embodiment of at least about0.1 percent by weight of the ink, and in yet another embodiment of atleast about 1 percent by weight of the ink, and in one embodiment of nomore than about 20 percent by weight of the ink, in another embodimentof no more than about percent by weight of the ink, and in yet anotherembodiment of no more than about 3 percent by weight of the ink,although the amount can be outside of these ranges.

The inks can also optionally contain a viscosity modifier. Examples ofsuitable viscosity modifiers include aliphatic ketones, such asstearone, and the like. When present, the optional viscosity modifier ispresent in the ink in any desired or effective amount, in one embodimentof at least about 0.1 percent by weight of the ink, in anotherembodiment of at least about 1 percent by weight of the ink, and in yetanother embodiment of at least about 10 percent by weight of the ink,and in one embodiment of no more than about 99 percent by weight of theink, in another embodiment of no more than about 30 percent by weight ofthe ink, and in yet another embodiment of no more than about 15 percentby weight of the ink, although the amount can be outside of theseranges.

Other optional additives to the inks include clarifiers, such as UNIONCAMP® X37-523-235 (commercially available from Union Camp), in an amountin one embodiment of at least about 0.01 percent by weight of the ink,in another embodiment of at least about 0.1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, tackifiers, such as FORAL® 85, a glycerol esterof hydrogenated abietic (rosin) acid (commercially available fromHercules), FORAL® 105, a pentaerythritol ester of hydroabietic (rosin)acid (commercially available from Hercules), CELLOLYN® 21, ahydroabietic (rosin) alcohol ester of phthalic acid (commerciallyavailable from Hercules), ARAKAWA KE-311 and KE-100 Resins,triglycerides of hydrogenated abietic (rosin) acid (commerciallyavailable from Arakawa Chemical Industries, Ltd.), synthetic polyterpeneresins such as NEVTAC® 2300, NEVTAC® 100, and NEVTAC® 80 (commerciallyavailable from Neville Chemical Company), WINGTACK® 86, a modifiedsynthetic polyterpene resin (commercially available from Goodyear), andthe like, in an amount in one embodiment of at least about 0.1 percentby weight of the ink, in another embodiment of at least about 5 percentby weight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 98 percent by weight of the ink, in another embodiment of no morethan about 75 percent by weight of the ink, and in yet anotherembodiment of no more than about 50 percent by weight of the ink,although the amount can be outside of these range, adhesives, such asVERSAMID® 757, 759, or 744 (commercially available from Henkel), in anamount in one embodiment of at least about 0.1 percent by weight of theink, in another embodiment of at least about 1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, plasticizers, such as UNIPLEX® 250(commercially available from Uniplex), the phthalate ester plasticizerscommercially available from Monsanto under the trade name SANTICIZER®,such as dioctyl phthalate, diundecyl phthalate, alkylbenzyl phthalate(SANTICIZER® 278), triphenyl phosphate (commercially available fromMonsanto), KP-140®, a tributoxyethyl phosphate (commercially availablefrom FMC Corporation), MORFLEX® 150, a dicyclohexyl phthalate(commercially available from Morflex Chemical Company Inc.), trioctyltrimellitate (commercially available from Eastman Kodak Co.), and thelike, in an amount in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 2percent by weight of the ink, and in one embodiment of no more thanabout 50 percent by weight of the ink, in another embodiment of no morethan about 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 10 percent by weight of the ink,although the amount can be outside of these ranges, and the like.

The ink compositions in one embodiment have melting points of no lowerthan about 50° C., in another embodiment of no lower than about 70° C.,and in yet another embodiment of no lower than about 80° C., and havemelting points in one embodiment of no higher than about 160° C., inanother embodiment of no higher than about 140° C., and in yet anotherembodiment of no higher than about 100® C., although the melting pointcan be outside of these ranges.

The ink compositions generally have melt viscosities at the jettingtemperature (in one embodiment no lower than about 75° C., in anotherembodiment no lower than about 100° C., and in yet another embodiment nolower than about 120° C., and in one embodiment no higher than about180° C., and in another embodiment no higher than about 150° C.,although the jetting temperature can be outside of these ranges) in oneembodiment of no more than about 30 centipoise, in another embodiment ofno more than about 20 centipoise, and in yet another embodiment of nomore than about 15 centipoise, and in one embodiment of no less thanabout 2 centipoise, in another embodiment of no less than about 5centipoise, and in yet another embodiment of no less than about 7centipoise, although the melt viscosity can be outside of these ranges.

The ink compositions can be prepared by any desired or suitable method.For example, the ink ingredients can be mixed together, followed byheating, to a temperature in one embodiment of at least about 100° C.,and in one embodiment of no more than about 140° C., although thetemperature can be outside of these ranges, and stirring until ahomogeneous ink composition is obtained, followed by cooling the ink toambient temperature (typically from about 20 to about 25° C.). The inksare solid at ambient temperature. In a specific embodiment, during theformation process, the inks in their molten state are poured into moldsand then allowed to cool and solidify to form ink sticks.

The inks can be employed in apparatus for direct printing ink jetprocesses and in indirect (offset) printing ink jet applications.Another embodiment disclosed herein is directed to a process whichcomprises incorporating an ink as disclosed herein into an ink jetprinting apparatus, melting the ink, and causing droplets of the meltedink to be ejected in an imagewise pattern onto a recording substrate. Adirect printing process is also disclosed in, for example, U.S. Pat. No.5,195,430, the disclosure of which is totally incorporated herein byreference. Yet another embodiment disclosed herein is directed to aprocess which comprises incorporating an ink as disclosed herein into anink jet printing apparatus, melting the ink, causing droplets of themelted ink to be ejected in an imagewise pattern onto an intermediatetransfer member, and transferring the ink in the imagewise pattern fromthe intermediate transfer member to a final recording substrate. In aspecific embodiment, the intermediate transfer member is heated to atemperature above that of the final recording sheet and below that ofthe melted ink in the printing apparatus. An offset or indirect printingprocess is also disclosed in, for example, U.S. Pat. No. 5,389,958, thedisclosure of which is totally incorporated herein by reference. In onespecific embodiment, the printing apparatus employs a piezoelectricprinting process wherein droplets of the ink are caused to be ejected inimagewise pattern by oscillations of piezoelectric vibrating elements.Inks as disclosed herein can also be employed in other hot melt printingprocesses, such as hot melt acoustic ink jet printing, hot melt thermalink jet printing, hot melt continuous stream or deflection ink jetprinting, and the like. Phase change inks as disclosed herein can alsobe used in printing processes other than hot melt ink jet printingprocesses.

Any suitable substrate or recording sheet can be employed, includingplain papers such as XEROX® 4024 papers, XEROX® Image Series papers,Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coatedpapers such as Sharp Company silica coated paper, JuJo paper, HAMMERMILLLASERPRINT® paper, and the like, transparency materials, fabrics,textile products, plastics, polymeric films, inorganic substrates suchas metals and wood, and the like.

Specific embodiments will now be described in detail. These examples areintended to be illustrative, and the claims are not limited to thematerials, conditions, or process parameters set forth in theseembodiments. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE I

To a 500 milliliter round bottom flask equipped with magnetic stir barwas added 13.5 grams of p-aminophenylacetic acid (obtained from TCIAmerica, Portland Oreg.), 8.7 grams of leucoquinizarin (obtained fromAceto Corp., Lake Success, N.Y.), 12.9 grams of quinizarin (obtainedfrom Aceto Corp.), 5.4 grams of boric acid (obtained from AldrichChemical Co., Milwaukee, Wis.), and 120 grams of ethanol. The flask wasplaced under stirring and a condenser in a hot oil bath at 120° C. for19 hours. Thereafter, the mixture was allowed to cool to roomtemperature. The resulting precipitated solids were collected by vacuumfiltration, recrystallized in n-butanol, and dried overnight in a vacuumoven. Yield: 19.2 grams of a compound believed to be of the formula

EXAMPLE Ia

To a 250 milliliter round bottom flask equipped with magnetic stir barwas added 5 grams of the compound prepared in Example I, 4 grams ofstearyl alcohol (ALFOL 18, obtained from Condea Vista, Austin Tex.), 70grams of xylene, and 2 drops of FASCAT 4202 catalyst (obtained from ElfAtochem North America Inc., Philadelphia, Pa.). The flask was placedunder stirring and a condenser and Dean Stark trap in a hot oil bath at150° C. for 6 hours. Thin layer chromatography (TLC) by normal phase in10 percent methanol in toluene showed a peak corresponding to thestarting material as well as a peak corresponding to the product,indicating that the reaction was not complete. An additional 2 grams ofstearyl alcohol and an additional 2 drops of FASCAT 4202 catalyst wereadded to the reaction mixture and the mixture was allowed to reflux foran additional 19 hours, after which TLC indicated that the reaction wasstill not complete. Thereafter, 0.5 grams of p-toluene sulfonic acid(additional catalyst; obtained from Boliden Intertrade Inc., Atlanta,Ga.) was added to the mixture and the reaction mixture was refluxed foran additional 6 hours, after which TLC indicated that the reaction wascomplete. Thereafter the solvent was distilled off and the product wascollected. It is believed that the product was of the formula

The spectral strength of the product was determined using aspectrophotographic procedure based on the measurement of the colorantin solution by dissolving the product in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the product was measured as about 14,275 mLAbsorbance Units per gram at absorption λ_(max) (535 nm).

EXAMPLE IIb

To a 3-neck 500 milliliter round-bottom flask with mechanical stirrerand constant pressure addition funnel, all placed in a 45° C. oil bath,was added 2.0 grams of the ester obtained in Example IIa and 25milliliters of glacial acetic acid (obtained from Aldrich Chemical Co.,Milwaukee, Wis.), after which stirring and heating were carried out for5 minutes. 2.10 grams of bromine (obtained from Aldrich Chemical Co.)was then added dropwise over 5 minutes. The reaction mixture wasthereafter heated and stirred for 15 additional minutes, cooled to roomtemperature, and poured into a 1 liter beaker containing 500 millilitersof methanol. The solid brominated product was filtered and washed withabout 250 milliliters of additional methanol and allowed to dry. 1.77grams of product were obtained. It is believed that this product was ofthe formula

EXAMPLE IIIa

A compound of the formula

was prepared as described in Example I. Thereafter, to a 250 milliliterround bottom flask equipped with magnetic stir bar was added 5 grams ofthe compound thus formed, 12.5 grams of UNILIN 700 alcohol (linear chainalcohol with an average of about 50 carbon atoms: obtained from BakerPetrolite Corp., Sugarland, Tex.), 70 grams of xylene, and a spatula tipfull of p-toluene sulfonic acid. The flask was placed under stirring anda condenser and Dean Stark trap in a hot oil bath at 150° C. for 48hours. TLC showed a peak corresponding to the starting material as wellas a peak corresponding to the product, indicating that the reaction wascomplete. Thereafter the solvent was distilled off and the product wascollected. It is believed that the product was of the formula

wherein n had an average value of about 49. The spectral strength of theproduct was determined using a spectrophotographic procedure based onthe measurement of the colorant in solution by dissolving the product intoluene and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the product wasmeasured as about 3,835 mL Absorbance Units per gram at absorptionλ_(max) (538 nm).

EXAMPLE IIIb

To a 3-neck 500 milliliter round-bottom flask with mechanical stirrerand constant pressure addition funnel, all placed in a 45° C. oil bath,was added 3.03 grams of the ester obtained in Example IIIa and 25milliliters of glacial acetic acid (obtained from Aldrich Chemical Co.),after which stirring and heating were carried out for 5 minutes. 4.4grams of bromine (obtained from Aldrich Chemical Co.) was then addeddropwise over 5 minutes. The reaction mixture was thereafter heated andstirred for about 15 additional minutes, cooled to room temperature, andpoured into a 1 liter beaker containing 500 milliliters of methanol. Thesolid product was filtered and collected. The product was then slurriedin a 1 percent NaOH/water solution and again filtered and allowed todry. 2.87 grams of product were obtained. TLC indicated muchunbrominated starting material, so the material was transferred to a 500milliliter 3-neck flask and 25 milliliters of glacial acetic acid wasadded and the mixture was heated to 100° C. 4.49 grams of bromine wasadded over 8 minutes and the reaction mixture was heated for anadditional 25 minutes before cooling. The reaction mixture was thenpoured into a 1 liter beaker containing 500 milliliters of methanol. Thesolid brominated product was filtered and collected. 2.66 grams ofproduct was obtained that by TLC appeared to be brominated. It isbelieved that this product was of the formula

wherein n had an average value of about 49.

EXAMPLE IVa

To a 250 milliliter round bottom flask equipped with magnetic stir baris added 5 grams of the compound formed in Example I, 4 grams of dimerdiol (PRIPOL 2033, available from Uniqema, New Castle, Del.), 70 gramsof xylene, and 2 drops of FASCAT 4202 catalyst (available from ElfAtochem North America Inc., Philadelphia, Pa.). The flask is placedunder stirring and a condenser and Dean Stark trap in a hot oil bath at150° C. for 48 hours. Thin layer chromatography (TLC) by normal phase in10 percent methanol in toluene is used to indicate reaction completion.Thereafter the solvent is distilled off and the product is collected. Itis believed that the product will be of the formula

wherein C₃₆H_(62+m) is a branched alkylene group which may includeunsaturated and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4,5, 6, 7, 8, 9, or 10, and wherein it is believed that at least some ofthe monomers will be of the formula

EXAMPLE IVb

To a 3-neck 500 milliliter round-bottom flask with mechanical stirrerand constant pressure addition funnel, all placed in a 45° C. oil bath,is added 2.0 grams of the ester obtained in Example IVa and 25milliliters of glacial acetic acid (available from Aldrich ChemicalCo.), after which stirring and heating are carried out for 5 minutes.2.10 grams of bromine (available from Aldrich Chemical Co.) is thenadded dropwise over 5 minutes. The reaction mixture is thereafter heatedand stirred for about 15 additional minutes, cooled to room temperature,and poured into a 1 liter beaker containing 500 milliliters of methanol.The solid brominated product is filtered and washed with about 250milliliters of additional methanol and is allowed to dry. It is believedthat the product will be of the formula

wherein C₃₆H_(62+m) is a branched alkylene group which may includeunsaturations and cyclic groups, wherein m is an integer of 0, 1, 2, 3,4, 5, 6, 7, 8, 9, or 10, and wherein it is believed that at least someof the monomers will be of the formula

EXAMPLE Va

To a 250 milliliter round bottom flask equipped with magnetic stir baris added 5 grams of the compound formed in Example I, 8 grams ofoctadecyl amine (ARMEEN 18 D, available from Akzo Nobel Chemicals Inc.,McCook, Ill.), 70 grams of xylene, and 2 drops of FASCAT 4202 catalyst(available from Elf Atochem North America Inc., Philadelphia, Pa.). Theflask is placed under stirring and a condenser and Dean Stark trap in ahot oil bath at 150° C. for 48 hours. Thin layer chromatography (TLC) bynormal phase in 10 percent methanol in toluene is used to determinereaction completion. Thereafter, the solvent is distilled off and theproduct is collected. It is believed that the product will be of theformula

EXAMPLE Vb

To a 3-neck 500 milliliter round-bottom flask with mechanical stirrerand constant pressure addition funnel, all placed in a 45° C. oil bath,is added 2.0 grams of the amide obtained in Example Va and 25milliliters of glacial acetic acid (available from Aldrich ChemicalCo.), after which stirring and heating are carried out for 5 minutes.2.10 grams of bromine (available from Aldrich Chemical Co.) is thenadded dropwise over 5 minutes. The reaction mixture is thereafter heatedand stirred for about 15 additional minutes, cooled to room temperature,and poured into a 1 liter beaker containing 500 milliliters of methanol.The solid product is filtered and washed with about 250 milliliters ofadditional methanol and allowed to dry. It is believed that the productwill be of the formula

EXAMPLE VI

An ink base was prepared by melting, admixing, and filtering thefollowing ingredients:

-   -   polyethylene wax (PE 655, obtained from Baker Petrolite, Tulsa,        Okla., of the formula CH₃(CH₂)₅₀CH₃), 42.01 parts by weight;    -   stearyl stearamide wax (KEMAMIDE® S-180, obtained from Crompton        Corporation, Greenwich, Conn.), 18.82 parts by weight;    -   tetra-amide resin obtained from the reaction of one equivalent        of a C-36 dimer acid obtained from Uniqema, New Castle, Del.        with two equivalents of ethylene diamine and UNICID® 700        (obtained from Baker Petrolite, Tulsa, Okla., a long chain        hydrocarbon having a terminal carboxylic acid group), prepared        as described in Example 1 of U.S. Pat. No. 6,174,937, the        disclosure of which is totally incorporated herein by reference,        24.99 parts by weight;    -   urethane resin obtained from the reaction of two equivalents of        ABITOL® E hydroabietyl alcohol (obtained from Hercules Inc.,        Wilmington, Del.) and one equivalent of isophorone diisocyanate,        prepared as described in Example 1 of U.S. Pat. No. 5,782,966,        the disclosure of which is totally incorporated herein by        reference, 8.82 parts by weight; urethane resin that is the        adduct of three equivalents of stearyl isocyanate and a        glycerol-based alcohol, prepared as described in Example 4 of        U.S. Pat. No. 6,309,453, the disclosure of which is totally        incorporated herein by reference, 5.21 parts by weight; and    -   NAUGUARD® 445 antioxidant (available from Uniroyal Chemical Co.,        Middlebury, Conn.), 0.15 parts by weight.

Thereafter, two inks were prepared by admixing different amounts of thedye prepared in Example I with the ink base thus prepared. The dye andink base in each case were added to a 140 milliliter beaker and heatedin an oven at 135° C. until molten. Subsequently, the beaker wasinserted in an oil heating bath at 135° C. and the contents of thebeaker were stirred for 45 minutes, followed by pouring the contentsinto aluminum pans and allowing the ink thus prepared to solidify. Ink 1contained 0.5 grams of the dye and 22.02 grams of the ink base. Ink 2contained 0.8 grams of the dye and 17.22 grams of the ink base.

Dynamic Viscosity is a material property which is used to characterizethe resistance to flow, with high numbers indicating high resistance.The dynamic viscosity of the inks was measured using a stress-controlledDynamic Stress Rheometer (DSR) 2000 from Rheometric Scientific (now TAInstruments). Geometry was 40 mm diameter Cone and Plate. A stress of 1Pascal was constantly maintained during a step-stress experiment, andviscosity data points were gathered at an approximate rate of 0.5 pointsper second. Each measurement lasted approximately 5 minutes, with anequilibration period of about 80 seconds; subsequently, data measuredbetween 100 and 300 seconds were averaged. The dynamic viscosity of Ink1 at 140° C. was 10.51 millipascal seconds (centipoise) and the dynamicviscosity of Ink 2 at 140° C. was 10.72 milliPascal seconds(centipoise).

The spectral strength of the inks were determined using aspectrophotographic procedure based on the measurement of the ink insolution by dissolving the ink in toluene and measuring the absorbanceusing a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. The spectralstrength of Ink 1 was measured as about 324 mL Absorbance Units per gramat absorption λ_(max) of 535 nanometers, and the spectral strength ofInk 2 was measured as about 633 mL Absorbance Units per gram atabsorption λ_(max) of 535 nanometers.

EXAMPLE VII

Two inks were prepared by admixing different amounts of the dye preparedin Example II with the ink base prepared in Example VI by the methoddescribed in Example VI. Dynamic viscosity and spectral strength ofthese inks were measured as described in Example VI. Ink 3 contained 3.0grams of the dye and 29.93 grams of the ink base, and exhibited adynamic viscosity at 140° C. of 10.88 millipascal seconds (centipoise)and a spectral strength of about 355 mL Absorbance Units per gram atabsorption λ_(max) of 535 nanometers. Ink 4 contained 4.0 grams of thedye and 17.95 grams of the ink base, and exhibited a dynamic viscosityat 140° C. of 11.52 milliPascal seconds (centipoise) and a spectralstrength of about 700 mL Absorbance Units per gram at absorption λ_(max)of 535 nanometers.

EXAMPLE VIII

The inks prepared in Examples VI and VII were used to generate prints onHAMMERMILL LASERPRINT® paper using a K Printing Proofer (manufactured byRK Print Coat Instrument Ltd., Litlington, Royston, Heris, SG8 0OZ,U.K.). In this method, the tested inks were melted onto a stainlesssteel printing plate which featured engraved 3.75 inch by 1.9 inchrectangular patterns of different depth and profile, allowing differentamounts of ink to accumulate in these areas, hence generatingrectangular prints with different ink coverage during the printingprocess, the printing plate being set at 150° C. temperature. A rollerbar fitted with the paper was then rolled over the plate containing themelted ink on its surface. The ink on the paper was cooled, resulting inthree separated images of rectangular blocks. Fingerprint diffusiontests were then carried out on the prints having the highest and lowestdegrees of ink coverage by having a test person rub fingers two timeswith fragrance-free LUBRIDERM® hand lotion. After each rub, the fingerswere dried with a towel. The surfaces of the prints were thencontaminated by touching them with the fingers, exerting an equal andmoderate pressure. Thereafter, the prints were placed into manilafolders with sheets of paper between the samples and maintained at roomtemperature for five days, after which the prints were inspected forchanges. The results indicated that the dyes prepared in Example II wereparticularly resistant to fingerprint diffusion.

EXAMPLE IX

Prints were generated with the inks prepared in Examples VI and VII bythe method described in Example VIII. SCOTCH® brand transparent tape wasthen attached to the prints in such a way that it simultaneously coveredprinted and unprinted areas of the prints. After attachment of the tape,the prints were placed into manila folders with sheets of paper betweenthe samples and placed in an oven at 60° C. for five days, after whichthe prints were inspected for changes. The results indicated that thedyes prepared in Example II were particularly resistant to tapediffusion.

1. A phase change ink composition comprising a phase change ink carrierand a colorant compound of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group, an arylene group, an arylalkylenegroup, or an alkylarylene group, provided that no oxygen atom creates a

linkage, x is —O— or —NR₃— wherein R₃ is a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, or an alkylaryl group, and R₂is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group.
 2. An ink according to claim 1 wherein Y is ahydrogen atom.
 3. An ink according to claim 1 wherein n is
 0. 4. An inkaccording to claim 1 wherein n is
 2. 5. An ink according to claim 1 ofthe formula


6. An ink according to claim 5 of the formula


7. An ink according to claim 5 of the formula


8. An ink according to claim 1 wherein R₁ is an alkylene group.
 9. Acompound according to claim 8 wherein R₁ is an unsubstituted alkylenegroup.
 10. An ink according to claim 8 wherein R₁ is a substitutedalkylene group.
 11. An ink according to claim 8 wherein R₁ is analkylene group wherein hetero atoms selected from oxygen, nitrogen,sulfur, silicon, phosphorus, or mixtures thereof are present in thealkylene group.
 12. An ink according to claim 8 wherein R₁ is analkylene group wherein no hetero atoms are present in the alkylenegroup.
 13. An ink according to claim 1 wherein R₁ is an arylene group.14. An ink according to claim 13 wherein R₁ is an unsubstituted arylenegroup.
 15. An ink according to claim 13 wherein R₁ is a substitutedarylene group.
 16. An ink according to claim 13 wherein R₁ is an arylenegroup wherein hetero atoms selected from oxygen, nitrogen, sulfur,silicon, phosphorus, or mixtures thereof are present in the arylenegroup.
 17. An ink according to claim 13 wherein R₁ is an arylene groupwherein no hetero atoms are present in the arylene group.
 18. An inkaccording to claim 1 wherein R₁ is an arylalkylene group or analkylarylene group.
 19. An ink according to claim 18 wherein R₁ is anunsubstituted arylalkylene or alkylarylene group.
 20. An ink accordingto claim 18 wherein R₁ is a substituted arylalkylene or alkylarylenegroup.
 21. An ink according to claim 18 wherein R₁ is an arylalkylene oralkylarylene group wherein hetero atoms selected from oxygen, nitrogen,sulfur, silicon, phosphorus, or mixtures thereof are present in eitherthe alkyl portion or the aryl portion or both of the arylalkylene oralkylarylene group.
 22. An ink according to claim 18 wherein R₁ is anarylalkylene or alkylarylene group wherein no hetero atoms are presentin the arylalkylene or alkylarylene group.
 23. An ink according to claim1 wherein R₁ is —CH₂—.
 24. An ink according to claim 1 wherein X is —O—.25. An ink according to claim 1 wherein X is —NR₃—.
 26. An ink accordingto claim 25 wherein R₃ is a hydrogen atom.
 27. An ink according to claim1 wherein R₂ is a hydrogen atom.
 28. An ink according to claim 27wherein X is —O—.
 29. An ink according to claim 27 wherein X is —NR₃—.30. An ink according to claim 29 wherein R₃ is a hydrogen atom.
 31. Anink according to claim 1 wherein R₂ is an alkyl group.
 32. An inkaccording to claim 31 wherein R₂ is an unsubstituted alkyl group.
 33. Anink according to claim 31 wherein R₂ is a substituted alkyl group. 34.An ink according to claim 31 wherein R₂ is an alkyl group wherein heteroatoms selected from oxygen, nitrogen, sulfur, silicon, phosphorus, ormixtures thereof are present in the alkyl group.
 35. An ink according toclaim 31 wherein R₂ is an alkyl group wherein no hetero atoms arepresent in the alkyl group.
 36. An ink according to claim 1 wherein R₂is an aryl group.
 37. An ink according to claim 36 wherein R₂ is anunsubstituted aryl group.
 38. An ink according to claim 36 wherein R₂ isa substituted aryl group.
 39. An ink according to claim 36 wherein R₂ isan aryl group wherein hetero atoms selected from oxygen, nitrogen,sulfur, silicon, phosphorus, or mixtures thereof are present in the arylgroup.
 40. An ink according to claim 36 wherein R₂ is an aryl groupwherein no hetero atoms are present in the aryl group.
 41. An inkaccording to claim 1 wherein R₂ is an arylalkyl group or an alkylarylgroup.
 42. An ink according to claim 41 wherein R₂ is an unsubstitutedarylalkyl or alkylaryl group.
 43. An ink according to claim 41 whereinR₂ is a substituted arylalkyl or alkylaryl group.
 44. An ink accordingto claim 41 wherein R₂ is an arylalkyl or alkylaryl group wherein heteroatoms selected from oxygen, nitrogen, sulfur, silicon, phosphorus, ormixtures thereof are present in the arylalkyl or alkylaryl group.
 45. Anink according to claim 41 wherein R₂ is an arylalkyl or alkylaryl groupwherein no hetero atoms are present in the arylalkyl or alkylaryl group.46. An ink according to claim 1 wherein at least one of R₂ and R₃ isother than hydrogen and the total number of carbon atoms in R₂+R₃ is atleast about
 8. 47. An ink according to claim 1 wherein at least one ofR₂ and R₃ is other than hydrogen and the total number of carbon atoms inR₂+R₃ is at least about
 12. 48. An ink according to claim 1 wherein atleast one of R₂ and R₃ is other than hydrogen and the total number ofcarbon atoms in R₂+R₃ is at least about
 18. 49. An ink according toclaim 1 wherein the colorant is of the formula


50. An ink according to claim 1 wherein the colorant is of the formula


51. An ink according to claim 1 wherein the colorant is of the formula


52. An ink according to claim 1 wherein the colorant is of the formula


53. An ink according to claim 1 wherein the colorant is of the formula

wherein n has an average value of about
 49. 54. An ink according toclaim 1 wherein the colorant is of the formula

wherein n has an average value of about
 49. 55. An ink according toclaim 1 wherein the colorant is of the formula


56. An ink according to claim 1 wherein the colorant is of the formula


57. A phase change ink composition comprising a phase change ink carrierand a colorant compound of the formula

wherein Y and Y′ each, independently of the other, are a hydrogen atomor a bromine atom, n and n′ each, independently of the other, is aninteger of 0, 1, 2, 3, or 4, R₁ and R₁′ each, independently of theother, is an alkylene group, an arylene group, an arylalkylene group, oran alkylarylene group, provided that no oxygen atom creates a

linkage, X and X′ each, independently of the other, is —O— or —NR₃—wherein each R₃, independently of the other, is a hydrogen atom, analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and R₂ is an alkylene group, an arylene group, an arylalkylene group, oran alkylarylene group.
 58. An ink according to claim 57 wherein thecolorant is of the formula

wherein C₃₆H_(62+m) is a branched alkylene group which may includeunsaturated and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4,5, 6, 7, 8, 9 or
 10. 59. An ink according to claim 57 wherein thecolorant is of the formula


60. An ink according to claim 57 wherein the colorant is of the formula


61. An ink according to claim 57 wherein the colorant is of the formula


62. An ink according to claim 57 wherein n and n′ are each
 0. 63. An inkaccording to claim 57 wherein n and n′ are each
 2. 64. An ink accordingto claim 57 wherein Y and Y′ are both hydrogen atoms.
 65. An inkaccording to claim 57 wherein R₁ and R₁′ are both unsubstituted alkylenegroups.
 66. An ink according to claim 57 wherein R₁ and R₁′ are both—CH₂—.
 67. An ink according to claim 57 wherein X and X′ are both —O—.68. An ink according to claim 57 wherein X and X′ are both —NR₃—.
 69. Anink according to claim 57 wherein R₂ is an alkylene group.
 70. An inkaccording to claim 69 wherein R₂ is an unsubstituted alkylene group. 71.An ink according to claim 69 wherein R₂ is a substituted alkylene group.72. An ink according to claim 69 wherein R₂ is an alkylene group whereinhetero atoms selected from oxygen, nitrogen, sulfur, silicon,phosphorus, or mixtures thereof are present in the alkylene group. 73.An ink according to claim 69 wherein R₂ is an alkylene group wherein nohetero atoms are present in the alkylene group.
 74. An ink according toclaim 57 wherein R₂ is an arylene group.
 75. An ink according to claim74 wherein R₂ is an unsubstituted arylene group.
 76. An ink according toclaim 74 wherein R₂ is a substituted arylene group.
 77. An ink accordingto claim 74 wherein R₂ is an arylene group wherein hetero atoms selectedfrom oxygen, nitrogen, sulfur, silicon, phosphorus, or mixtures thereofare present in the arylene group.
 78. An ink according to claim 74wherein R₂ is an arylene group wherein no hetero atoms are present inthe arylene group.
 79. An ink according to claim 57 wherein R₂ is anarylalkylene group or an alkylarylene group.
 80. An ink according toclaim 79 wherein R₂ is an unsubstituted arylalkylene or alkylarylenegroup.
 81. An ink according to claim 79 wherein R₂ is a substitutedarylalkylene or alkylarylene group.
 82. An ink according to claim 79wherein R₂ is an arylalkylene or alkylarylene group wherein hetero atomsselected from oxygen, nitrogen, sulfur, silicon, phosphorus, or mixturesthereof are present in either the alkyl portion or the aryl portion orboth of the arylalkylene or alkylarylene group.
 83. An ink according toclaim 79 wherein R₂ is an arylalkylene or alkylarylene group wherein nohetero atoms are present in the arylalkylene or alkylarylene group. 84.A phase change ink composition comprising a phase change ink carrier anda colorant compound comprising three or more moieties of the formula

wherein each Y, independently of the others, is a hydrogen atom or abromine atom, each n, independently of the others, is an integer of 0,1, 2, 3, or 4, each R₁, independently of the others, is an alkylenegroup, an arylene group, an arylalkylene group, or an alkylarylenegroup, provided that no oxygen atom creates a

linkage, and each X, independently of the others, is —O— or —NR₃—wherein each R₃, independently of the others, is a hydrogen atom, analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group.85. An ink according to claim 1 wherein the phase change ink carriercomprises a monoamide, a tetra-amide, or a mixture thereof.
 86. An inkaccording to claim 1 wherein the phase change ink carrier comprises (a)stearyl stearamide, (b) a dimer acid based tetra-amide that is thereaction product of dimer acid, ethylene diamine, and stearic acid, or(c) mixtures thereof.
 87. An ink according to claim 1 wherein the phasechange ink carrier comprises (a) stearyl stearamide, (b) a dimer acidbased tetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid having at least about 36 carbon atoms, or(c) mixtures thereof.
 88. An ink according to claim 87 wherein thecarboxylic acid has at least about 40 carbon atoms, and wherein thecarboxylic acid has no more than about 200 carbon atoms.
 89. An inkaccording to claim 1 wherein the phase change ink carrier comprises anisocyanate-derived material.
 90. An ink according to claim 1 wherein thephase change ink carrier comprises a urethane isocyanate-derivedmaterial, a urea isocyanate-derived material, a urethane/ureaisocyanate-derived material, or mixtures thereof.
 91. An ink accordingto claim 1 wherein the phase change ink carrier comprises a mixture ofone or more amides and one or more isocyanate-derived materials.
 92. Anink according to claim 1 wherein the phase change ink carrier comprisesone or more materials selected from paraffins, microcrystalline waxes,polyethylene waxes, ester waxes, amide waxes, fatty acids, fattyalcohols, fatty amides, sulfonamide materials, tall oil rosins, rosinesters, ethylene/vinyl acetate copolymers, ethylene/acrylic acidcopolymers, ethylene/vinyl acetate/acrylic acid copolymers, copolymersof acrylic acid with polyamides, ionomers, and mixtures thereof.
 93. Anink according to claim 1 wherein the phase change ink carrier is presentin the ink in an amount of at least about 0.1 percent by weight of theink and wherein the phase change ink carrier is present in the ink in anamount of no more than about 99 percent by weight of the ink.
 94. An inkaccording to claim 1 wherein the phase change ink carrier is present inthe ink in an amount of at least about 50 percent by weight of the inkand wherein the phase change ink carrier is present in the ink in anamount of no more than about 98 percent by weight of the ink.
 95. An inkaccording to claim 1 wherein the phase change ink carrier is present inthe ink in an amount of at least about 90 percent by weight of the inkand wherein the phase change ink carrier is present in the ink in anamount of no more than about 95 percent by weight of the ink.
 96. An inkaccording to claim 1 wherein the ink carrier comprises (a) apolyethylene wax, (b) a stearyl stearamide wax, (c) a dimer acid basedtetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid having at least about 36 carbon atoms,(d) a urethane resin derived from the reaction of two equivalents ofhydroabietyl alcohol and one equivalent of isophorone diisocyanate, (e)a urethane resin that is the adduct of three equivalents of stearylisocyanate and a glycerol-based alcohol, and (f) an antioxidant.
 97. Anink according to claim 1 wherein the ink carrier comprises (a) apolyethylene wax in an amount of at least about 25 percent by weight ofthe ink and in an amount of no more than about 60 percent by weight ofthe ink, (b) a stearyl stearamide wax in an amount of at least about 8percent by weight of the ink and in an amount of no more than about 32percent by weight of the ink, (c) a dimer acid based tetra-amide that isthe reaction product of dimer acid, ethylene diamine, and a carboxylicacid having at least about 36 carbon atoms in an amount of at leastabout 10 percent by weight of the ink and in an amount of no more thanabout 32 percent by weight of the ink, (d) a urethane resin derived fromthe reaction of two equivalents of hydroabietyl alcohol and oneequivalent of isophorone diisocyanate in an amount of at least about 6percent by weight of the ink and in an amount of no more than about 16percent by weight of the ink, (e) a urethane resin that is the adduct ofthree equivalents of stearyl isocyanate and a glycerol-based alcohol inan amount of at least about 2 percent by weight of the ink and in anamount of no more than about 13 percent by weight of the ink, and (f) anantioxidant in an amount of at least about 0.01 percent by weight of theink and in an amount of no More than about 1 percent by weight of theink.
 98. An ink according to claim 1 wherein the colorant is present inthe ink in an amount of at least about 0.1 percent by weight of the ink.99. An ink according to claim 1 wherein the colorant is present in theink in an amount of at least about 1 percent by weight of the ink. 100.An ink according to claim 1 wherein the colorant is present in the inkin an amount of at least about 3 percent by weight of the ink.
 101. Anink according to claim 1 wherein the colorant is present in the ink inan amount of no more than about 20 percent by weight of the ink.
 102. Anink according to claim 1 wherein the colorant is present in the ink inan amount of no more than about 13 percent by weight of the ink.
 103. Anink according to claim 1 wherein the colorant is present in the ink inan amount of no more than about 6 percent by weight of the ink.
 104. Anink according to claim 1 wherein the ink has a melting point of no lowerthan about 50° C. and wherein the ink has a melting point of no higherthan about 160° C.
 105. An ink according to claim 1 wherein the ink hasa melting point of no lower than about 70° C. and wherein the ink has amelting point of no higher than about 140° C.
 106. An ink according toclaim 1 wherein the ink has a melting point of no lower than about 80°C. and wherein the ink has a melting point of no higher than about 100°C.
 107. An ink according to claim 1 wherein the ink has a melt viscosityat a temperature of about 140° C. of no more than about 30 centipoise.108. An ink according to claim 1 wherein the ink has a melt viscosity ata temperature of about 140° C. of no more than about 20 centipoise. 109.An ink according to claim 1 wherein the ink has a melt viscosity at atemperature of about 140° C. of no more than about 15 centipoise. 110.An ink according to claim 1 wherein the ink has a melt viscosity at atemperature of about 140° C. of no less than about 2 centipoise.
 111. Anink according to claim 1 wherein the ink has a melt viscosity at atemperature of about 140° C. of no less than about 5 centipoise.
 112. Anink according to claim 1 wherein the ink has a melt viscosity at atemperature of about 140° C. of no less than about 7 centipoise.
 113. Anink according to claim 1 further containing a xanthene dye.
 114. An inkaccording to claim 113 wherein the xanthene dye is a rhodamine dye. 115.An ink according to claim 114 wherein the rhodamine dye is Solvent Red49.
 116. A process which comprises (1) incorporating into an ink jetprinting apparatus a phase change ink composition comprising a phasechange ink carrier and a colorant compound of the formula

wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1,2, 3, or 4, R₁ is an alkylene group, an arylene group, an arylalkylenegroup, or an alkylarylene group, provided that no oxygen atom creates a

linkage, X is —O— or —NR₃— wherein R₃ is a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, or an alkylaryl group, and R₂is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group; (2) melting the ink; and (3) causing droplets ofthe melted ink to be ejected in an imagewise pattern onto a substrate.117. A process according to claim 116 wherein the printing apparatusemploys a piezoelectric printing process wherein droplets of the ink arecaused to be ejected in imagewise pattern by oscillations ofpiezoelectric vibrating elements.
 118. A process according to claim 116wherein the substrate is a final recording sheet and droplets of themelted ink are ejected in an imagewise pattern directly onto the finalrecording sheet.
 119. A process according to claim 116 wherein thesubstrate is an intermediate transfer member and droplets of the meltedink are ejected in an imagewise pattern onto the intermediate transfermember followed by transfer of the imagewise pattern from theintermediate transfer member to a final recording sheet.
 120. A processaccording to claim 119 wherein the intermediate transfer member isheated to a temperature above that of the final recording sheet andbelow that of the melted ink in the printing apparatus.